Process of producing keto compounds from ketones and tetraalkyldiaminomethanes.



UNITED STATES P TENT OFFICE.

GEORGMERLING AND OTTO CHRZESCINSKI, OF ELBERFELD, AND HUGO KOHLER, OF -LEVERKUSEN, NEAR COLOGNE, GERMANY. ASSIGNORS T0 FARBENFABRIKEN VOBM. FBIEDR. BAYER 8c 00., OF ELBERFELD, GERMANY, A CORPORATION OF PROCESS OF PBODUCING-KETO COMPOUNDS FROM KETONES AND TETRAALKYL- Patented Apr. 21, 1914.

T 0 all whom it may concern:

Be it ,known that we, Gnono Mnnnmo,

OI-1o Cnnznscmsm, and HUGO K'c'urusn, doctors of philosophy, chemists, citizens of the German Empire, residing at, respectively, Elberfeld and Leverkusen, near Cologne-onthe-Rhin'e, Germany, have invented new and useful Improvements in Processes of Producing Keto Compounds from Ketones and Tetraalkyldiaminomethanes, of which the following is a specification.

The present invention concerns the production of keto compounds containing the radical:

which have proved to be valuable intermediate products for the manufacture of erythrene and its homologues.

The process for their production consists in treating ketones such as acetone and its homolo es with the homologues of tetramethyl iaminomethane e. g. tetraethyldiaminomethane either with or without condensing agents, such as caustic alkalis, alkali carbonates and bicarbonates, alkaline earths,

. aluminium hydrate, sodium phosphate, 01':

ganic bases and salts. The condensation proceeds although slowly even at ordinary temperature and without condensing agents and the presence or absence of water or of other solvents does not interfere with the reaction. Heating and condensing agents accelerate the reaction. The homologues of tetramethyldiaminomethanc can be used as such or as mixtures of formaldehyde and dialkylamin solutions in the proper molecular proportions. These reactions proceed e. 9. according to the following equation:

CH3CO-CH2(R)+(C9Ha)1NCHz-N(O2Hb Application filed May 16. 1913. Serial No. 788,072.

Besides this product ketodiamins of the formula:

are obtained for instance by the two-fold introduction of the residue cm N. 50.11,),

into the corresponding ketone. These ketodiamins can be separated from the ketomonoamins by fractional distillation.

In order to illustrate the new process more fully the following examples are given, the parts being by weight Example 1.Production of beta-acetylcthyldiethylamin and bcta-acetyltrimethylcnctetracthyldiamin from tetraet yldiaminomethane and acetone: 750iparts of aqueous formaldehyde (40 per cent.) are gradually dropped into 3245 parts of aqueous diethylamin solution per cent.) which is being stirred and cooled and 2000 parts of acetone, 400 parts of baryta-water (saturated at ordinary temperature) and 500 arts of water are then added. After 20 days heating from 2530 C. bicarbonate is added to the brown solution in order to remove the baryta. Barium carbonate is removed by filtration. The oil is separated with potash and dried over potash. The excess of acetone 1s removed by distillation cacao and the remammg mixture of bases 1s decomposed by a fractional distillation in vacuo to beta-acctyl-ethyldiethylamin and betaacetylti-imethylenetetraethyldiamin. The former base is a colorless oil havin an intense ammoniacal smell difiicultly soluble in water and boils at 7276 C. (16 mm.), the latter one represents a colorless and odorless oil with a little yellow coloration boiling at 95100 G. (7-8 mm.).

Example 2.-Production of beta-acetylpropyl-diethylamin cH -co-cH. (CH3) cH,- N. can

or beta-beta-acetyl-inethyltrimethylenctetraethyldiamin enrwcnnn from tetracthyldiaminoniethane and methylethylketone: 150 parts of an aqueous diethyl- :lllllll solution 2 molecules) are gradually dropped into 25 parts of aqueous formaldehyde (40 per cent., 1 molecule) while well stirred and cooled. This mixture forming two layers is mixed with 150 parts of methylethyllretone and boiled with the reflux condenser until a test portion after acidulating with arctic acid is not any more rendered turbid by a solution of anilin acetate which requires some hours. The solution is then dehydrated with potash and dried over potash. The excess of methylethylketone is now distilled off, advantageously under somewhat reduced pressure in an apparatus suitable for fractional distillation and the remaining mixture of bases is decomposed by a fractional distillation in 110mm to betaacetyl propyl diethylamin and beta betaacetyl lnethyltrimethylenetetraethyldiamin. The former represents a colorless oil with a little ammoniacal smell, difiicultly soluble in water boiling at 7778 C. (16 mm), the latter is a thick, yellowish, almost odorless oil which boils at 105-110 C. (7 mm.)

It will be seen that the above keto compounds contain the radical or nucleus graphically represented:

a co t C.IH'.'N \R where R is alkyl, e. 9., methyl, and R represents ethyl or its higher homologues.

In our copending application Serial No. 768071 we have claimed generically the use of the higher di'alkylaminomethane compounds for forming keto compoinids, such as those above described, and. we have also claimed specifically in that application the use of the higher dialkylaminooxymethanes; while the claims of the present application are drawn specifically to the use in this process of the higher tetraalkyldiaminomethanes.

o claim l. The process of producing a polyalkylamino substituted keto compound which comprises reacting on a ketone with tetraalkyldiaminomethane in which the alkyl groups contain more than one carbon atom until the two fold introduction of the dialkyl-aminomethyl radical has been effected.

2. The process of producing a dialkylamino substituted ketone which comprises reacting on a. ketone with tetraalkyldiarninomethane in which the alkyl' groups contain more ilian one carbon atom.

23. The process of producing a polyalkylamino ml stituted keto compound which comprises reacting on a ketone with tetraalkyldiaminomethane in which the alkyl groups contain more than one carbon atom with the addition of a condensing agent un til the two fold introduction of the dialliylaminomethyl radical has been effected.

J. The process of producing a. dialkylamino substituted keto compound which comprises reacting on a ketone with tetraalkyldiaminomethane in which the alkyl groups contain more than one carbon atom with the addition of a condensing agent.

5. The process of producing a polyalkylamino substituted keto compound which comprises reacting on a. ketonc with tetraalkyldiaminomethane in which the alkyl groups contain more than one carbon atom with the addition of an inorganic base as a condensing agent until the two fold introduction of the dialkyl-aminomethyl radical has been efiected.

6. The process of producing a polyalkylamino substituted ketone which comprises reacting on a ketone with tetraalkyldialninomethane in which the alkyl groups contain more than one carbon atom with the addition of an inorganic base as a condensing agent. I

7. The process of producing keto compounds containing the group:

ethyl cnheo on, 1-z which comprises treating a methyl ketone with tetraethyldiamino methane.

8. The process of producing pounds containing the group:

which comprises treating a methyl ketone with tetraethyldiaminomethane until a twofold introduction of the diethylaminomethyl radical has been effected.

9. The process of producing keto compounds containing the nucleus keto com- CHg-CO- which comprises treating a methylketone with tetraalkyldiaminomethane in which the alkyl groups contain more than one carbon atom with the additlon of an inorganic base as a condensing agent.

11. The process of producing keto -commtraethyldia minomethane with the addition pounds containing the radical of a condensing agent I I In testimony where'bf we have hereunto 15 f- (R'=thylwdn=alkyl) set our hands in the presence of two sub- 5 wh' h com es treating ketbne W'th scribing with 1c us a 1 ttraeth ldi minomethane. GEORG M LI -1 12. Tie process of producing keto-com- OTTO CHRZESCINSKI. [14. s.] pounds containing the radical or nucleus 7 HUGQ KOHLER [L 5.] n-,-co -ni-cn,-u (R'=ethylandR-slkyl) Witnesses: i

l HELEN Numm, which comprises treating a. ketone. with ALBERT Nun-.11.

Goplu of thin patent may be obtaifled for five cents each, by addressing the Commissioner at Patents, Washington, II. 0."

it is hereby certified that in Letters Patent No. 1,094,160, granted April 21, 1914, upon the application of Georg Merling and Otto Chrzescinskipof Elberfeld, and Hugo Kohler, of Leverkusen, near Cologne, Germany, foran improvement in Proceeses of Producing Kebo Compounds from Ketones and Tetrnalkyidiaminomethanes,

an error appears in the printed specification requiring correction as followsi Page 1,

line 43, second line offormula, second parentheses, for (C,H,) read ((AB and that the seid Letters Patent should he read with this correction therein thatthe some may conform to the record of the ease in the Patent Office.

Signed and seziled this 30th day of-Jnne, A. D, 1914. p

I i l R. F. WHITEHEAD,

[BELL] Acting Umnmieazkmer of Patents. 

